Polymers disulphides

Free formaldehyde is released from the above reaction, which in turn acts as a reducing agent on the polymer disulphide bonds to bring about a reduction into thiol with the formation of formic acid ... 

When sulphur is melted viscosity changes occur as the temperature is raised. These changes are due to the formation of long-chain polymers (in very pure sulphur, chains containing about 100 (X)0 atoms may be formed). The polymeric nature of molten sulphur can be recognised if molten sulphur is poured in a thin stream into cold water, when a plastic rubbery mass known as plastic sulphur is obtained. This is only slightly soluble in carbon disulphide, but on standing it loses its plasticity and reverts to the soluble rhombic form. If certain substances, for example iodine or oxides of arsenic, are incorporated into the plastic sulphur, the rubbery character can be preserved. 

By reduction in the degree of polymerisation. To produce processable rubbers the original polymers are masticated with substances such as benzothiazole disulphide and tetramethylthiuram disulphide. The more severe degradation techniques to produce liquid polysulphides are mentioned below. 

The first step in the manufacture of the foil involves the production of alkali cellulose. This is then shredded and allowed to age in order that oxidation will degrade the polymer to the desired extent. The alkali cellulose is then treated with carbon disulphide in xanthating chums at 20-28°C for about three hours. 

During emulsion polymerization, a high conversion of monomer to polymer produces cross-linked rubber which is insoluble. To obtain a high conversion in the polymerization reaction and a processable polymer, suitable polymer modification should be made. The use of sulphur moieties allows this goal to be reached [2]. Sulphur-modified polychloroprenes contain di- and polysulphide sequences in the polymer chains. After the polymerization reaches the desired degree, reaction is stopped by adding thiuram disulphide ... 

These polymers are very sensitive to mastication. Mastication decreases the solution viscosity and increases the ease of solution. Because the reactive sulphur linkages, rapid vulcanizing properties are obtained. On the other hand, the presence of thiuram disulphide improves the resistance of CR to dehydrochlorination. 

Another approach was developed by Scott in the 1970 s (7.8) which utilises the same mechanochemistry used previously by Watson to initiate the Kharacsh-type addition of substituted alkyl mercaptans and disulphides to olefinic double bonds in unsaturated polymers. More recently, this approach was used to react a variety of additives (both antioxidants and modifiers) other than sulphur-containing compounds with saturated hydrocarbon polymers in the melt. In this method, mechanochemically formed alkyl radicals during the processing operation are utilised to produce polymer-bound functions which can either improve the additive performance and/or modify polymer properties (Al-Malaika, S., Quinn, N., and Scott, 6 Al-Malaika, S., Ibrahim, A., and Scott, 6., Aston University, Birmingham, unpublished work). This has provided a potential solution to the problem of loss of antioxidants by volatilisation or extraction since such antioxidants can only be removed by breaking chemical bonds. It can also provide substantial improvement to polymer properties, for example, in composites, under aggresive environments. 

As mentioned previously, additive treatments involve the application of a polymer to the fibre. This is usually prepared before application and contains reactive groups. However, it is also possible to form the polymer in situ within the fibres. The traditional approach is to apply the polymer after a subtractive oxidation treatment but environmental concern over A OX problems is increasing demand for additive treatments that can stand alone. There is no denying that the oxidative step can facilitate subsequent treatment with a polymer, since the scission of cystine disulphide bonds to yield cysteic acid residues provides useful reactive sites for crosslinking or anchoring the polymer. 

The authors describe experiments on six NR compounds commonly used for latex gloves to determine the potential hazards of skin contact with reference to curing compounds and accelerators, including mercaptobenzthiazole and zinc dialkyldithiocarbamates. Simulation methods and the influence of a common hand disinfectant were investigated. In the case of tetramethylthiuram disulphide, it was discovered that decomposition products could be formed on the skin which are not present in the original rubber. 6 refs. Articles from this journal can be requested for translation by subscribers to the Rapra produced International Polymer Science and Technology. Accession no.849747... 

In some cases chain transfer agents are added to reaction mixture or to control the Molecular weight of the polymers. Mercaptans are used for this purpose. The modifying action of sulphur compounds is much greater than most of the solvents. The modifying action of diisopropylxanthate disulphide in the synthesis of SBR (styrene butadiene rubber) can be shown as under ... 

Alkyl and glycosyl isocyanates and isothiocyanates are produced in good yield under phase-transfer catalytic conditions using either conventional soluble catalysts or polymer-supported catalysts [32, 33]. Acyl isothiocyanates are obtained under similar conditions [34]. A-Aryl phosphoramidates are converted via their reaction with carbon disulphide under basic conditions into the corresponding aryl isothiocyanates, when the reaction is catalysed by tetra-n-butylammonium bromide [35]. 

Geometric effects coupled with diffusion and nucleation usually control the rates of all solids deposition phenomena. Such effects can be put to good use in the production of special products such as cellulose yarn (rayon), by the precipitation of cellulose in filament form as it emerges as sodium cellulose xanthate liquid from the spinnerets into a bath containing sulphuric acid, which extracts the sodium as sodium sulphate, and the carbon disulphide. In a similar manner, the fabrication of aromatic polyimide fibres is performed by dissolving the polymer in concentrated sulphuric acid and forcing the solution through spinnerets into water. 

All the major caseins associate with themselves and with each other. In unreduced form, K-casein is present largely as disulphide-linked polymers. K-Casein also forms hydrogen and hydrophobic bonds with itself and other caseins but these secondary associations have not been studied in detail. 

Watanabe, K. and Klostermeyer, H. 1976. Heat-induced changes in sulphydryl and disulphide levels of u-lactoglobulin A and the formation of polymers. J. Dairy Res. 43, 411, 418. 

Leitner,. V.M., Walker, G.F. and Bernkop-Schniirch, A. (2003b) Thiolated polymers evidence for the formation of disulphide bonds with mucus glycoproteins. Eur. 

A sustained drug release is favourable for drugs with short elimination half-life. It can be controlled by hydration and diffusion mechanisms or ionic interactions between the drug and the polymeric carrier. In the case of diffusion control the stability of the carrier system is essential, as its disintegration leads to a burst release. Therefore, the cohesiveness of the polymer network plays a crucial role in order to control the release over several hours. Due to the formation of disulphide bonds within the network thiomers offer adequate cohesive stability. Almost zero-order release kinetics could be shown for insulin embedded in thiolated polycarbophil matrices (Clausen and Bernkop-Schnurch 2001). In the case of peptide and protein drugs release can be controlled via ionic interactions. An anionic or cationic polymer has to be chosen depending... 

The Inifer technique enables us to fulfil some requirements of polymer architecture even in some radical processes. An amplified form may be applied, the Iniferter variant, where the radical initiator simultaneously acts as a transfer and terminating agent. Otsu et al. used sulphides and disulphides (tetraethylthiuram disulphide, PhSSPh, Ph2S, PhCH2SSCH2Ph) [96] and carbamates (benzyl-A,A-diethyldithiocarbamate, p-xylylene-A,7V-diethyl-dithiocarbamate) [97] in the photopolymerization of methyl methacrylate and styrene, and phenylazotriphenylmethane in the polymerization of methyl methacrylate [98]. Living radical polymerizations yield polymers with defined end groups or the required block copolymers. 

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